Process for dyeing synthetic polyamide textiles in the presence of organic sulphonic acids and basic nitrogen compounds

ABSTRACT

A level dyeing is obtained on fabric of synthetic polyamide fibers having a variable dyestuff affinity by treating the fabric at a temperature of from 70* to 130* C. in a liquor of which the pH value throughout is maintained between 3 and 5, said dye liquor containing an aqueous solution of a surface active compound containing sulphonic acid groups or a surface active sulphuric acid ester, e.g. a sulphated oil constituted by a high molecular weight fatty acid subjected to a high degree or an ester thereof, to which liquor there is then sequentially added, without cooling or going outside the stated pH value range, (i) a basic nitrogen containing compound, or a quaternized derivative thereof, which is an addition product of 20 to 200 mols of ethylene oxide to certain long chain non-cyclic amines defined hereinafter, and (ii), simultaneously or subsequently, an anionic dye which would normally dye said fabric giving a stripy appearance, e.g. a so-called milling acid dye, dyeing being then affected in the usual way.

United States Patent Mikula 1 Apr. 25, 1972 [5.4] PROCESS FOR DYEINGSYNTHETIC POLYAMIDE TEXTILES IN vTHE PRESENCE OF ORGANIC, SULPHONICACIDS AND BASIC NITROGEN COMPOUNDS [72] Inventor: Adam Mikula, Basle,Switzerland [73] Assignee: Sandog IJtd., Basle, Switzerland [22] Filed:Apr. 18, 1969 [21] Appl. No.: 817,568

[30] Foreign Application Priority Data Apr. 26, 1968 [52] U.S.Cl..8/l72, 8/173 [51] Int. Cl. ..'.D06p 5/06 [58] Field of Search ..8/l68,172,84, 85, 178

[56] References Cited UNITED STATES PATENTS 3,006,935 10/1961 Albrecht.;.8/85 X 3,071,427 1/1963 Buehler et al ..8/85 X Switzerland ..6293/683,230,029 1/1966 v Cappyccio et al. ..8/l68 3,391,985 7/1968 Zurbuchen6! al ..8/84 X Primary Examiner-George F. Lesmes Assistant Examiner-T.J. Herbert, Jr. Attorney-Wenderoth, Lind & Ponack [5 7] ABSTRACT A leveldyeing is obtained on fabric of synthetic polyamide fibers having avariable dyestuff affinity by treating the fabric at a temperature offrom 70 to 130 C.' in a liquor of which the pH value throughout ismaintainedbetween 3 and 5,'said dye liquor containing an aqueoussolution of a surface active compound containing sulphonic acid groupsor a surface active sulphuric acid ester, e.g. a sulphated oilconstituted by a high molecular weight fatty acid subjected to a highdegree or an ester thereof, to which liquor there is then sequentiallyadded,

7 Claims, No Drawings lt is known to dye textile material of syntheticpolyamide fibers having variable dyestuff affinity in such a wayas toproduce dyeings of level appearance by treating said material beforedyeing with an aqueous solution at a pH value of from 3 to 4 andtemperatures of preferably 70 to 80 C., said solution containing asulphated high molecular weight fatty acid or a sulphate ester thereof,if desired in admixture with ethoxylated amines having a high molecularweight fatty acid residue. In carrying out the pretreatment in thisk'nown dyeing process, the pretreatment bathis cooled to 50 C. and thedye and an acid binding agent are only added after such cooling,

whereupon dyeing is effected at the boil. Thus relatively much heatenergy and time are required for this known process.

It has now been found that it is possible to dye synthetic polyamidefibers in level shades and having an especially pretty aspect by meansof the process of the present invention, described in detailhereinafter, in which process the dyestuff is added to the pretreatmentliquor without cooling that liquor.

The present invention thus provides a process for the level dyeing of atextile material of synthetic polyamide fibers having a variabledyestuff affinity with an anionic dye which would normally cause saidmaterial to have a stripy appearance, which process comprises firsttreating the material to be dyed with an aqueous solution of a surfaceactive compound selectedfrom the class consisting of surface activesulphuric acid esters and surface active sulphonic acid group containingsubstances in a pretreatment bath, then adding to said bath with thetextile material still in it, without cooling, a

material selected from the class consisting of basic nitrogen containingcompounds and quaternized such compounds, said compounds containing atleast one non-cyclic radical with 12 to 30 carbon atoms, and at least 20200 ethenoxy groups, and the dyestuff, and finally effecting dyeing, theentire process being effected at a temperature of from 70 to 130 and apH value of from 3 to 5. It will be appreciated that the basic nitrogencontaining compound may contain more than one nitrogen atom and thenon-cyclic radical may be saturated or unsaturated; the last mentionedradical, which preferably contains 16 24 carbon atoms, may (but neednot) contain one or more hetero atoms or groups with hetero atoms, e.g.O, Sor- CONH. H

Examples of said surface active compounds are alkylarylsulphonic acids,alkanesulphonic acids, aminoalkylsulphonic acid amides of high molecularweight fatty acids sulphated high molecular weight fatty acids or theiresters, e.g.. sulphation products of oleic, elaidic or ricinoleic acidand their esters, especially alkyl ones, for example the methyl, ethyl,propyl or butyl ester, or the glycerine ester of these fatty acids, forexample castor oil. Sulphation products having a high degree ofsulphation, preferably those with a sulphation degree above 70 percent,are especially suitable. Examples of the basic nitrogen containingcompounds are those having the following formulae l-lV:-

wherein each of R and R is independently selected ffom' The classconsisting of saturated and unsaturated, non-cyclic radicals with 12 to30, preferably 16 to 24, carbon atoms,

R, is selected from the class consisting of saturated and unsaturatednon-cyc'lic radicals withfrom one to 30 carbon atoms,

each of A A and A is independently selected from the class consisting ofpolyethenoxy chains, withthe proviso that the sum of the ethenoxy groupsin all three chains must be at least 20 and at most 200,

each of A, and A, is independently selected from the class consisting ofpolyethylene oxide chains, withthe proviso that the sum of the ethenoxygroups for the two chains mustbe at least 20 and at most 200,

at least one of X X and X is independently selected from the classconsisting of monosubstituted ethylene groups sub stituted with at leastone of alkyl and hydroxyalkyl residues having one to 20 carbon atoms andphenyl residues, disubstituted ethylene groups substituted with apolymethylene chain, and disubstituted ethylene groups substituted with2 non-cyclic, saturated residues each containing from one to 18 carbonatoms (e. g. alkyl radicals), v

and any remaining symbol X X and X is independently selected from theclass consisting of single bonds, monosubstituted ethylene groupssubstituted with at least one of alkyl and hydroxyalkyl residues havingone to 20 carbon atoms and phenyl residues, disubstituted ethylenegroups substituted with a polymethylene chain, and disubstitutedethylene groups substituted with 2 non-cyclic, saturated residues eachcontaining from one to l8 carbon atoms (e.g. alkyl radicals),

n represents an integer selected from 1, 2, 3, 4, 5 and 6,

and m represents an integer selected from i, 2, 3, 4, 5, 6 and 7. It isto be noted that R, R, and R may contain hetero atoms or groups ofhetero atoms, e.g. O, S or -CO- Nl-l-; these three symbols may, however,be aliphatic v radicals. I

The above and other suitable compounds are described, for example, inSwiss Pat. Nos. 317,900, 353,013, 363,006, 373,012, 388,903, 40l,900 and409,991.

Especially suitable are the addition products of ethylene oxide or ofpropylene oxide and ethylene oxide to high molecular weight monoorpolyarnines, for example, oleyl-, cetyl-,' stearylandbehenylaminoethylamine or -propylamine and their quaternizationproducts.

The ethoxylated amines may be used either as such or in the form oftheir quaternization products. Suitable quaternization agents are, forexample, dimethylsulphate, diethylsulphate, methyl chloride, benzylchloride, methylor ethylbenzene sulphonate, methylorethylpara-methylbenzene sulphonate etc. Depending on the amount ofquaternization agent used, it is possible to quaternize one, several orall of the basic nitrogen atoms.

The pretreatment is effected with a liquor of which the pH value hasbeen adjusted to from 3 to 5 by means of an acid such as, for example,acetic acid, formic acid or sulphuric acid and may last about 10 to 30minutes.

The amount of the said surface active compound may be, for example, from0.5 to 5 percent of the weight of the fibers; in general, however, 0.7to 2 percent are sufficient. The amount of the basic compound which maybe used is likewise from 0.5 to 5 percent of the weight of the fibers,preferably however about 0.7 to 1.5 percent thereof. All these quantitydata relate to percent of active substance. The dyeing may be effectedat the boil or at temperatures above 100 C. at superatrnosphericpressure.

' Examples of dyestuffs which normally lead to a stripy appearance inthe dyeing of synthetic polyamide fiber textilearmethylaminosulphonylphenylazo)-2-hydroxynaphthalene, the so-calledmilling acid dyes, for example l,4-bis-[4'-(4- chlorophenoxy)-2-sulphophenylamino]-anthraquinone or 1-hydroxy-2-(2-phenoxy-5'-chlorophenylazo)-8-(4"-methylphenylsulphonylamino)-naphthalene-3,6-disulphonic acid, and theacid dyes for wool such as l-amino-2-bromo-4- (4-methylphenylamino)-anthraquinone-Z-sulphonic acid.

These give level dyeings of good light and wash fastness in accordancewith the process of the invention.

One preferred basic nitrogen containing compound is an addition productof 90 to l mols of ethylene oxide to 1 mol of C ,-alkyl-3-propylamine.

It is to be noted that the dyestuff may be added simultaneously with orsubsequently to said basic nitrogen containing compound orquaternization product thereof.

In the following Examples parts are parts by weight, percentages arepercentages by weight and the temperatures are stated in degreesCentigrade.

EXAMPLE 1 100 parts of a fabric of Nylon-66 which would normally dyewith a stripy appearance are treated for 30 minutes in 4,000 parts of aboiling aqueous liquor of which the pH valve has been adjusted to 4-5 bymeans of acetic acid and which contains 3.3 parts of castor oilsulphated to 80 percent containing 30 percent of active substance.Thereafter 1.4 parts of an addition product of 100 mols of ethyleneoxide and 1 mol of behenylamino-3-propylamine are added to the liquorwithout cooling it. 1 part of the acid dye Blue 127 (61135), Color Indexll 1956, is then added to the boiling liquor and dyeing is effected for1 hour. A level blue dyeing is obtained which is level and fast towashing, perspiration and light.

Instead of using the above sulphated castor oil it is possible to use,with a similar success, the same amount of oleic acid which has beensulphated to 95 percent, or 1.8 parts of 75 percent sodium salt ofdibutylnaphthalenesulphonic acid or 1.4 parts of 98 percent sodium saltof dodecylbenzenesulphonic acid.

Similar effects are likewise obtained when, instead of the ethoxylatedbehenylaminopropylamine, there is used the same amount of an additionproduct of 30 mols ethylene oxide to 1 mol of monocetylor monstearylaminoethylaminoethylamine or to l mol of a mixture of fatty amines with18-22 carbon atoms in the alkyl radical, or the same amount of anaddition product of 20 mols ethylene oxide to 1 mol coconut amine, orthe same amount of 25-80 mols of ethylene oxide to 1 mol of oleyl-,cetyl-, or stearylamine, or the same amount of 90-120 mols ethyleneoxide to 1 mol of eicosyl-, docosylor tetracosylamine, or the sameamount of 80-200 mols ethylene oxide to 1 mol of hexadecyl-, octadecyl-,eicosyl-, docosylor tetracosyl-3-aminopropylamine.

Using the same method of dyeing, very good dyeings are likewise obtainedwith a lz2-cobalt complex compound of l- (2 '-hydroxy-3 '-acetylamino-5-methylphenylazo )-2-hydroxy- S-nitrobenzene or of1-(2-hydroxy-5-methylaminosulphonylphenylazo)-2-hydroxynaphthalene, orwith a 1:2-chromium complex compound ofl-(3'-chlorophenyl)-3-methyl-4-(2-carboxy-4-aminosulphonylphenylazo)-5-pyrazolone, of a-(2' -hydroxy-5'-amino-sulphonylphenylazo )-aceto-acetylaminooctane, ofl-(4'-cyanophenyl)-3-methyl-4-(2-hydroxy-4'-methylaminosulphonylphenylazo)-5-pyrazolone or of l-(2-hydroxy-S'-methylsulphonylphenylazo)-2-hydroxy-8-acetylaminonaphthalene, or with any one of the following dyes:l-amino-4-(2',4,6-trimethylphenylamino)-anthraquinone-2-sulphonic acid,l-amino-4-phenylamino-anthraquinone-2-sulphonic acid, l,4-bis-( 2 ,4',6-trimethyl-3 sulphophenylamino)-anthraquinone,l-(4'-(4"-cyclohexylphenoxy)-phenylazo)-2-(2"',4',6"-trimethylphenylamino)-8-hydroxy-naphthalene-6,2'-disulphonicacid, 1-amino-2-(4'-amylphenoxy)-4-(2",4",6"-trimethylphenylamino)-anthraquinone-2,3"-disulphonicacid or l-acetyl-2- hydroxy-4-methyl-6-(4'-chlorophenyl-amino)-3-azobenzanthrone-Z'-sulphonic acid.

Similar effects are obtained by using 1.4 parts of 85 percent sodiumsalt of the methyltauride of oleic acid instead of the sulphated castoroil.

EXAMPLE 2 100 parts of a Nylon-6 fabric which would normally dye with astripy appearance are treated for 30 minutes in 3,000 parts of a boilingaqueous liquor of which the pH value has been adjusted t0'4-5 by meansof acetic acid and which contains 4 parts of castor oil which has beento percent and has an active substance content of 30 percent.

Without cooling the liquor, 1.4 parts of an addition product of 90 molsethylene oxide to 1 mol arachinyl-3- aminopropylamine are then added andthe nylon fabric is agitated in the liquor for about 5 minutes. Againwithout cooling, 1 part ofthe dyestuff Acid Blue 1 13 (26360), ColorIndex II 1956, is then added and dyeing is effected at the boil for 1hour. In this way a level, blue dyeing is obtained which is free ofstripes and has a good fastness to light and washing.

Instead of the ethoxylated arachinylaminopropylamine it is also possibleto use with similar success the same amount of a quatemized additionproduct (which can be obtained according to Example VI of Swiss Pat. No.388,903) of mols of ethylene oxide to 1 mol of the addition product of 2mols of propylene oxide to 1 mol of the alkylaminopropylamine theredescribed.

In Examples 1 and 2 the dyestuff can be added at the same time as eachof the ethylene oxide addition products with similar effect as regardsthe dyeing obtained.

Although the present invention is described herein with particularreference to specific details, it is not intended that such detailsshall be regarded as limitations upon the scope of the invention exceptinsofar as included in the accompanying claims.

I claim:

1. A process for the level dyeing of a textile material of syntheticpolyamide fibers having a variable dyestuff affinity with an anionic dyewhich would normally cause said material to have a stripy appearance,which process comprises first treating the material to be dyed with anaqueous solution of a surface active compound selected from the classconsisting of alkylarylsulphonic acids, alkanesulphonic acids,aminoalkylsulphonic acid amides of high molecular weight fatty acids,sulphated high molecular weight fatty acids and esters thereof, to thepretreatment bath, then adding to said bath with the textile materialstill in it, without cooling, a material selected from the classconsisting of basic nitrogen containing compounds, said compoundsselected from the following formulae l to IV:

wherein each of R and R, is independently selected from the classconsisting of saturated and unsaturated, non-cyclic radicals with 12 to30, preferably 16 to 24, carbon atoms, R, is selected from the classconsisting of saturated and unsaturated non-cyclic radicals with fromone to 30 carbon atoms,

each of A A, and A is independently selected from the class consistingof polyethenoxy chains, with the proviso that the sum of the ethenoxygroups in all three chains must be at least and at most 200, each of Aand A, is independently selected from the class 5 consisting ofpolyethylene oxide chains, with the proviso that the sumof the ethenoxygroups for the two chains must be at least 20 and at most 200, at leastone of X,, X, and X is independently selected from the class consistingof monosubstituted ethylene groups substituted with at least one ofalkyl and hydroxyalkyl residues having one to 20 carbon atoms and phenylresidues, disubstituted ethylene groups substituted with a polymethylenechain, and disubstituted ethylene groups substituted with 2 non-cyclic,saturated residues each containing from one to 18 carbon atoms, and anyremaining symbol X X and X is independentlyselected from the classconsisting of single bonds, monosubstituted ethylene groups substitutedwith at least 20 one of alkyl and hydroxyalkyl residues having one to 20carbon atoms and phenyl residues, disubstituted ethylene groupssubstituted with a polymethylene chain, and disubstituted ethylene.groups substituted with 2non-cyclic, saturated residues each containingfrom one to 18 carbon atoms,

n represents an integer selected from 1, 2, 3, 4, 5 and 6, and mrepresents an integer selected from 1, 2, 3, 4, 5, 6

and 7,

' and quatemized such compounds and the dyestuff, and

finally effecting dyeing, the entire process being effected at atemperature of from 70 to 130 C. and a pH value of from 3 to 5.

2. A process according to claim 1, in which the pretreatment is effectedwith a solution of a sulphated castor oil of which the sulphation degreeamounts to at least 70 percent.

3. A process according to claim 1, in which the pretreatment iseffectedwith a solution of a sulphated oleic acid of which the sulphationamounts to at least 95 percent.

4. A process according to claim 1, in which said lgasic nitrogencontaining compound is an addition product of 90 to 100 mols of ethyleneoxide to 1 mol of C -alkyl- 3propylarnine.

5. A process according to claim 1, in which the pretreatment and theadding of the dye are effected at the boiling temperature of the liquor.

6. A process according to claim 1, in which the pretreatment is effectedat a pH value of 4.5 to 5.

'7. A process according to claim 1, in which dyeing is effected with atleast one milling acid dye.

UNITED STATES PATENT @FFIEE @ETWMAWE' H CREQHN Patent No. 3,658,4 0Dated April 25., 1972 Inventorh!) Adam Mikula It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown'below:

The name of the assignee in Item [73] on page 1 of the subject patentshould read "Sandoz Ltd."

Signed and sealed this 17th day of October 1972.

(SEAL) Attest:

EDWARD M.FLETGHER,JRQ ROBERT GOT'I'SCHALK Attesting Officer Commissionerof Patents FdHM PO-1050 (10-69) USCOMM-DC 60376-P69 us. GOVERNMENTPRINTING OFFICE: 1969 oass:3a

2. A process according to claim 1, in which the pretreatment is effectedwith a solution of a sulphated castor oil of which the sulphation degreeamounts to at least 70 percent.
 3. A process according to claim 1, inwhich the pretreatment is effected with a solution of a sulphated oleicacid of which the sulphation amounts to at least 95 percent.
 4. Aprocess according to claim 1, in which said basic nitrogen containingcompound is an addition product of 90 to 100 mols of ethylene oxide to 1mol of C20-22-alkyl-3propylamine.
 5. A process according to claim 1, inwhich the pretreatment and the adding of the dye are efFected at theboiling temperature of the liquor.
 6. A process according to claim 1, inwhich the pretreatment is effected at a pH value of 4.5 to
 5. 7. Aprocess according to claim 1, in which dyeing is effected with at leastone milling acid dye.